Production of vat dyestuffs



Patented Jan. 19, 1932 UNITED STATES PATENT OFFICE MAX ALBERT KUNZ, OFMANNHEIM, AND KARL KOBERLE, OF LUDWIGSHAFEN-ON-THE- RHINE, GERMANY,ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK,

N. 'Y., A CORPORATION OF DELAWARE PRODUCTION or VAT mrnsrnrrs NoDrawing. Original application filed June 16, 1927, Serial No. 199,420,and in Germany July 8. 1926.

Divided and this application filed July 28, 1928.

The subject matter of the present application has been divided out fromour copending application for the manufacture of vat dyestuffs, Ser. No.199,420, filed June 16, 1927, and relates tothe manufacture of vatdyestuffs which are considered to be halogenatedallo-ms-naphthodianthrones.

We have found that new halogeniferous vat dyestuffs are obtained whenhalogen is introduced into the allo-ms-naphthodianthrones which may beobtained by subjecting a 2.2-dimethyl-ms-benzdianthrone to the action ofagents with an alkaline reaction and which we regard to be compoundscontaining the system.

The new dyestuffs are distinguished from the allo-ms-naphthodianthroneswhich are free from halogen by their deeper color which mostly issubstantially more reddish, and by their excellent aflinity. Moreover,these new products are of great interest not only as vat dyestuffs, butalso as intermediate products for the manufacture of other vatdyestuffs.

The introduction of halogen may be effected in various ways. Forexample, halogen, or agents liberating the same, may be allowed to acton the dyestuffs in the presence or absence of atalysts. Suitablecatalysts for t llS purpose are, for example, iodine,

sulfur, metals and metallic salts. The reac- Serial No. 296,085.

tion is preferably carried on in solvents or diluents.

For purification, the afore-described halogenatedallo-ms-naphthodianthrones may be recrystallized from solvents of highboiling point, or may be treated, in paste form, with hypochlorite. Theyusually give green solutions in concentrated sulfuric acid and furnish,with an alkaline hydrosulfite solution,

blue-violet vats from which orange to scarlet I dyeings are obtained oncotton,

We have also found that the properties of the halogeniferous vatdyestuffs can be substantially improved by introducing several differenthalogens into the allo-ms-naphthodianthrones. This is eifected bytreating the said anthrone derivatives with different halogens eitherconcurrently or successively, for example, with chlorine and. bromine,or suitable agents which liberate halogens, and preferably in thepresence of solvents or diluents and in presence or absence ofhalogen-transferrers. The introduction of different halogens into theallo-ms-naphthodianthrones may also be effected by introducing into suchhalogen-allo-ms-naphthodianthrones which are still capable of taking upmore halogen, another halogen, which differs from that already containedin the original substance, the said introduction being carried out inthe manner already described. This process furnishes excellent yields.The resulting dyestufi's give brilliant scarlet to red dyeings on cottonfrom a blue-violet vat. For example the dichlor-dibrom-allo-.rs-naphthodianthrone prepared by this procss dyes cotton a considerablyfaster and reeper red than is obtained from tetrabron'ello-ms-naphthodianthrone. Apart from the valuable shade, the resultingdyestufis also display, in many cases, surprisingly improved propertiesas regards fastness.

The following examples will further explain the nature of the inventionwhich however is not restricted to these examples. The parts are byweight.

Ewample 1 1 part of allo-ms-naphthodianthrone obtainable according toExample 1 of our copending application Ser. No. 199,420 is dissolved in10 to 12 parts of nitrobenzene, whereupon 0.1 put of iodine is added and1% parts of sulfuryl chlorid are stirred in, drop by drop, at C.Stirring is cont'nme d for a further 6 hours whereupon the allowed tocool and the dichlor-alloms-naphthodianthrone separated in crystallineform is filtered oil by suction. It dissolves to a green solution inconcentrated sulfuric acid, and can be recovered therefrom, as an orangepaste, by precipitation with water. It gives orange dyeings on cottonfrom a violet vat.

Emample 2 A oarmtoif dry chlorine is passed tor an hour fllrough aboiling solution of 1 part of allo-ms-inapbthodianthrone in 10 parts oftrickles-benzene to which 0.1 part of iodine has been added. The solventis then expelled with steam, and the residue is preferably disadeed inconcentrated sulfuric acid and precipitated therefrom by dilution. There- 511% product has the same properties as that mined in Example 1.

, Example 3 Ervample 4 1 part of dichlor-allo-ms-naphthodianthroneobtainable according to Example 4 of our copending application Ser. No.199,420 is dimoived in 10 to 12 parts of nitrobenzene, 3. parts ofbromine being then stirred in, drop by drop, at 160 0., this temperaturebeing maintained for 4 hours and the dyestufl filtered by suction whencold. It gives violet reed dyeings on cotton from a violet vat.

Example 5 1 part of allo-ms-naphthodianthrone is dissolved in 10 partsof nitrobenzene, 0.05

' part of iron filings being then added. The

temperature is raised to 160 C. and 2 parts of bromine are added bydrops. After stirring for 4 hours at the same temperature, the mixtureis treated as in Example 3. The resulting dyestuif which is atetrabrom-alloms-naphthodianthrone gives brilliant red dyeings on cottonfrom a violet vat.

Example 6' 10 parts of chlor-allo-ms-naphthodianthrone (the dyestufi' ofExample 1) are dissolved in 100 parts of nitrebenzene and after additionof 1 part of iron filings are stirred with 19 parts of bromine at 160C., the stirring being continued at the same tem rature until theevolution of hydrogen romide ceases in about 6 to 8 hours. The dyestufi,which is filtered after cooling, and according to analysis is adichlor-dibrom derivative, forms a brown-red powder which dissolves to agreen solution in concentrated sulfuric acid. Brilliant red dyeings areobtained from a bluish-violet vat.

What we claim is 2-- 1. The process of producing new vat dyestuffs whichcomprises subjecting a dyestufi containing the system (anallo-ms-naphthodianthrone) to the action of a halogenating agent.

2. The process of producing new vat dyestufi's which comprisessubjecting an allo-msnaphthodianthrone in a diluting medium and in thepresence of a halogen transferrer to the action of a halogenating agent.

3. The rocess of producing new vat dyestufls which comprises subjectingan alloms-naphthodianthrone to the action of agents introducingdifferent halogen atoms into the dyestufi molecule.

4. The process of producing new vat dyestufl's which comprisessubjecting a halogenallo-ms-naphthodianthrone capable of being furtherhalogenated, to the action of a halogenating agent, the halogen of whichis diffierent from that contained in the dyestuff.

5. As new articles of manufacture, vat dyestuffs which are halogenatedallo-msnashthodianthrones which give violet vats and green solutions inconcentrated sulfuric aci 6. As new articles of manufacture vatdyestufi's which are allo-ms-naphthodianthrones containing at least twodifferent halogen atoms which give green solutions in concentratedsulfuric acid and bluish-violet vats. 7 As new articles of manufacturevat dyestuffs which are allo-ms-naphthodianthrones containing chlorineand bromine which give green solutions in concentrated sulfuric acid andbluish-Violet vats.

' 8. As new articles of manufacture dichlor- 1clibrom-allo-1ns-naphthodianthrones dissolving to green solutions inconcentrated sulfuric acid and giving a bluish-violent Vat.

In testimony whereof, We affix our signatures.

' MAX ALBERT KUNZ.

KARL KGBERLE.

